CN103305570B - Method for pre-treating corn stalks by diluted hydrochloric acid auxiliary oxide morpholine-N-oxide - Google Patents
Method for pre-treating corn stalks by diluted hydrochloric acid auxiliary oxide morpholine-N-oxide Download PDFInfo
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- CN103305570B CN103305570B CN201310224202.XA CN201310224202A CN103305570B CN 103305570 B CN103305570 B CN 103305570B CN 201310224202 A CN201310224202 A CN 201310224202A CN 103305570 B CN103305570 B CN 103305570B
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Abstract
The invention relates to a method for pre-treating corn stalks by diluted hydrochloric acid auxiliary oxide morpholine-N-oxide, which belongs to the field of chemical engineering. The method comprises the following steps of: carrying out dissolving pre-treatment for 0.5 hour-2 hours on corn stalks at 90 DEG C-120 DEG C in an NMMO (Oxide Morpholine)-diluted hydrochloric acid-water pre-treatment system; adding deionized water to wash and regenerate to obtain a cellulose material; washing the regenerated cellulose material by the deionized water by three times, adding an acetic acid-sodium acetate buffer solution to form a mixed system; and carrying out enzymolysis by using cellulose, and carrying out an oscillatory reaction on a constant-temperature shaking table with the speed of 180 rpm at 50 DEG C to achieve the enzymolysis purpose of corn stalks. According to the method for pre-treating corn stalks by diluted hydrochloric acid auxiliary oxide morpholine-N-oxide disclosed by the invention, the diluted hydrochloric acid auxiliary oxide morpholine-N-oxide is utilized to pre-treat the corn stalks, so that the high-value utilization of the corn stalks is realized, and the reducing sugar yield is bigger than 60%. The method for pre-treating corn stalks by diluted hydrochloric acid auxiliary oxide morpholine-N-oxide has the advantages of being simple in process, high in efficiency, economical in process, less in the three wastes, and the like.
Description
Technical field
The invention discloses a kind of dilute hydrochloric acid assisted oxidation morpholine-
nthe method of-oxide compound (NMMO) pre-treatment maize straw, belongs to field of chemical engineering.
Background technology
Along with socioeconomic development, energy consumption gets more and more, and due to the finiteness of fossil oil and non-renewable, biomass energy became the focus that people pay close attention to gradually in recent years.Scholarly forecast, biomass energy will become the important component part of following continuous energy, and by 2015, global total energy consumption will have 40% from biomass energy.Tellurian cellulose resource is very abundant, and China's agricultural crop straw ultimate production is more than 700,000,000 tons, and maize straw effectively utilizes the energy dilemma of cellulose resource to facing mankind realistic meaning.
The main component of Woody Biomass is Mierocrystalline cellulose, hemicellulose and xylogen.Cellulosic structure is complicated, have higher degree of crystallinity, Mierocrystalline cellulose inside exists a large amount of crystalline texture and intermolecular and intramolecular hydrogen bond, cause solvent and reaction reagent very low to cellulosic accessibility, this becomes the bottleneck of constraints on fiber element recycling.Therefore, pre-treatment is had to pass through before cellulosic material saccharification.Existing pretreatment process mainly contains the multiple methods such as physics, chemistry, biology, or the combination of aforesaid method, and wherein chemical method and Physical are the research emphasis of various countries investigator.Electroplating effluent recycling and mainly uses alkali, mineral acid, organic solvent and oxygenant etc. as pretreating reagent.In organic solvent preprocessing process, with an organic solvent or the mixing solutions of organic solvent and inorganic acid catalyst can destroy connecting key between the xylogen of fibrous material inside and hemicellulose.
At present, morpholine oxide-
n-oxide compound (NMMO) can dissolving cellulos raw material effectively as efficient pre-treatment solvents.Research shows, NMMO energy dissolving cellulos is the high polarity due to N-O key, can destroy cellulosic hydrogen bond network and form new hydrogen bond with solute, and then can pretreatment of fiber element raw material.NMMO can not only be miscible with water, and can dissolved lignin's Molecular fragments well.Our seminar finds to utilize the mixed solution of NMMO and a small amount of dilute hydrochloric acid as pretreating reagent, xylogen can be separated with carbohydrate, substantially increase the conversion coefficient of cellulosic material.
Summary of the invention
The technical issues that need to address of the present invention be open dilute hydrochloric acid assisted oxidation morpholine-
nthe method of-oxide compound (NMMO) pre-treatment maize straw, realizes the efficiently saccharifying of maize straw.
A kind of dilute hydrochloric acid assisted oxidation morpholine of the present invention-
nthe method of-oxide compound (NMMO) pre-treatment maize straw, carry out in accordance with the following steps:
(1) pre-treatment and saccharification maize straw:
In NMMO-dilute hydrochloric acid-water pretreatment system, after dissolving pre-treatment 0.5-2 h being carried out to maize straw under 90-120 ° of C after NMMO and 0.5%-10% (w/w) the dilute hydrochloric acid mixing of 85% (w/w), add deionized water wash regeneration and obtain cellulosic material; After the cellulose materials deionized water wash regenerated three times, add pH=4.8 acetic acid-sodium acetate buffer solution (50 mM) and form mixed system, corn stalk fiber element raw material final quality concentration is 20%, then enzymolysis is carried out with the cellulase that whole mass concentration is 0.3%, oscillatory reaction on the constant-temperature table of 50 ° of C and 180 rpm, can reach the object of enzymolysis maize straw.
Wherein the mass ratio of NMMO and maize straw is 20:1.
beneficial effect of the present invention:
A kind of dilute hydrochloric acid assisted oxidation morpholine of the present invention-
nthe method of-oxide compound (NMMO) pre-treatment maize straw, the advantages such as pretreatment condition gentleness, process economy, the three wastes are few.Maize straw reaches good pretreating effect.
Accompanying drawing explanation
Fig. 1 cellulase saccharification pre-treatment maize straw progress curve.■ reducing sugar glucose
Embodiment
The content of reducing sugar is analyzed with 3,5-dinitrosalicylic acid (DNS).Reducing sugar yield=concentration of reduced sugar × 100%/maize straw concentration.
The content of glucose utilizes liquid chromatography (HPLC) to analyze.Glucose yield=glucose concn × 100%/maize straw concentration.
embodiment 1dilute hydrochloric acid (0.5% w/w) assists NMMO pre-treatment maize straw
In pretreatment system, after the maize straw of 2 g dryings utilizes NMMO thing and 0.5% (w/w) dilute hydrochloric acid of 85% (w/w) to carry out dissolving pre-treatment 2 h under 90 ° of C, add deionized water wash regeneration.After the cellulose materials deionized water wash regenerated three times, add pH=4.8 acetic acid-sodium acetate buffer solution (50 mM) and form mixed system, corn stalk fiber element raw material final quality concentration is 20%, then enzymolysis is carried out with the cellulase that whole mass concentration is 0.3%, oscillatory reaction 72 h on the constant-temperature table of 50 ° of C and 180 rpm, reducing sugar yield is 65.4%.
embodiment 2dilute hydrochloric acid (10% w/w) assists NMMO pre-treatment maize straw
In pretreatment system, after the maize straw of 2 g dryings utilizes NMMO and 10% (w/w) dilute hydrochloric acid of 85% (w/w) to carry out dissolving pre-treatment 0.5 h under 120 ° of C, add deionized water wash regeneration.After the cellulose materials deionized water wash regenerated three times, add pH=4.8 acetic acid-sodium acetate buffer solution (50 mM) and form mixed system, corn stalk fiber element raw material final quality concentration is 20%, then carry out enzymolysis with the cellulase that whole mass concentration is 0.3%, oscillatory reaction on the constant-temperature table of 50 ° of C and 180 rpm, saccharification proceeding results as shown in Figure 1, significantly do not suppress in saccharifying, react 72 h, reducing sugar yield is 70.8%, and glucose yield is 37.0%.
Claims (1)
1. dilute hydrochloric acid assisted oxidation morpholine-
nthe method of-oxide compound (NMMO) pre-treatment maize straw, is characterized in that carrying out in accordance with the following steps:
(1) pre-treatment and saccharification maize straw:
In NMMO-dilute hydrochloric acid-water pretreatment system, after dissolving pre-treatment 0.5-2 h being carried out to maize straw under 90-120 ° of C after NMMO and 0.5%-10% (w/w) the dilute hydrochloric acid mixing of 85% (w/w), add deionized water wash regeneration and obtain cellulosic material; After the cellulosic material deionized water wash regenerated three times, add pH=4.8, concentration is that the acetic acid-sodium acetate buffer solution of 50 mM forms mixed system, corn stalk fiber element raw material final quality concentration is 20%, then enzymolysis is carried out with the cellulase that whole mass concentration is 0.3%, oscillatory reaction on the constant-temperature table of 50 ° of C and 180 rpm, can reach the object of enzymolysis maize straw;
Wherein the mass ratio of NMMO and maize straw is 20:1.
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| CN201310224202.XA CN103305570B (en) | 2013-06-07 | 2013-06-07 | Method for pre-treating corn stalks by diluted hydrochloric acid auxiliary oxide morpholine-N-oxide |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103774479B (en) * | 2013-12-31 | 2016-04-13 | 广州甘蔗糖业研究所 | NMMO/DMSO mixed solvent is utilized to extract the method for biomass cellulose |
| CN105985993A (en) * | 2015-02-13 | 2016-10-05 | 中国石油天然气股份有限公司 | Pretreatment method of corn straw |
| CN105985992B (en) * | 2015-02-13 | 2019-09-03 | 中国石油天然气股份有限公司 | Method for treating corn straws by using N-methyl-N-morpholine oxide in steam explosion system |
| CN110257456A (en) * | 2019-07-18 | 2019-09-20 | 吉林农业大学 | A kind of maize straw pretreatment method based on sulfamic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001074906A1 (en) * | 2000-03-31 | 2001-10-11 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Method for producing and processing a cellulose solution |
| CN101899487A (en) * | 2009-09-16 | 2010-12-01 | 青岛生物能源与过程研究所 | Method for in-situ enzymolysis and recovery of cellulose system |
| CN102604844A (en) * | 2012-04-16 | 2012-07-25 | 常州大学 | Galactomyces and method of in-situ cellulose enzymolysis using same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001074906A1 (en) * | 2000-03-31 | 2001-10-11 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Method for producing and processing a cellulose solution |
| CN101899487A (en) * | 2009-09-16 | 2010-12-01 | 青岛生物能源与过程研究所 | Method for in-situ enzymolysis and recovery of cellulose system |
| CN102604844A (en) * | 2012-04-16 | 2012-07-25 | 常州大学 | Galactomyces and method of in-situ cellulose enzymolysis using same |
Non-Patent Citations (1)
| Title |
|---|
| 化学预处理对玉米秸秆酶解糖化效果的影响;宋安东等;《化学与生物工程》;20060831;第23卷(第8期);摘要和第33页结论部分 * |
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Effective date of registration: 20201116 Address after: No.008 Zijing Avenue, Chahe Town Industrial Park, Pizhou City, Xuzhou City, Jiangsu Province Patentee after: Jiangsu Yikun Medical Technology Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |